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I. MALFANT

Mise en ligne effectuee par Isabelle Malfant


Molécules et Composites pour l’Optique (MCO)


Equipe "Molécules et Composites pour l’Optique"

Permanents

Isabelle Malfant, Professeur, UPS, Responsable d’équipe
isabelle.malfant chez lcc-toulouse.fr
+33 5 61 33 31 01

Pascal G. Lacroix, Directeur de Recherche CNRS
pascal.lacroix chez lcc-toulouse.fr
+33 5 61 33 31 88

Kathleen Moineau, Directrice de Recherche CNRS
kathleen.chane chez lcc-toulouse.fr
+33 5 61 33 31 88

Isabelle Sasaki, Chargée de Recherche CNRS
isabelle.sasaki chez lcc-toulouse.fr
+33 5 61 33 31 88

Bénédicte de Bonneval, Maître de Conférences, UPS
benedicte.debonneval chez lcc-toulouse.fr
+33 5 61 33 31 52

Marine Tasse, Technicienne chimiste
marine.tasse chez lcc-toulouse.fr
+33 5 61 33 31 52

Non-Permanents (présents en septembre 2014)

Joëlle Akl, doctorante MESR
+33 5 61 33 31 12

Daniel Hernandez Maldonado, doctorant, bourse Mexique
+33 5 61 33 31 12

Damien Leborgne, doctorant, bourse PRES/Région
+33 5 61 33 31 66

Chunxiang Chen, doctorante, bourse Chine
+33 5 61 33 31 12

Hasan Shamran Mohammed, doctorant, bourse Campus France/Irak
+33 5 61 33 31 12

Bianca X. Valderrama G., doctorante, Mexique
+33 5 61 33 31 66

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Anciens membres

The design and characterization of new molecular photoactive materials are at the heart of our group. The materials currently under consideration have mainly interesting properties for optical storage (photochromic), photovoltaics (electron donors and acceptors) and the nonlinear optical switching. Our studies are located on the border of two key themes : photonics and organic electronics. New developments are also dealing with photodynamic therapy.

Keywords : Ruthenium complexes - Nitrosyl ligand - Optical data storage - Photodynamic Therapy - Two Photon Absorption- Non linear Optics - Molecular Switching - Photochromism - Organic Photovoltaïcs - Ni bis-dithiolene complexes - Donor small molecules

Ruthenium Nitrosyl Systems

The ruthenium nitrosyl complexes offer a large variety of physical-chemical properties. In particular, they are of great interest in optical data storage as well as for therapeutic applications.

NO Photorelease

The ruthenium nitrosyl complexes have the property to release NO upon irradiation which is very important for therapeutic applications. Indeed, the NO molecule (Nobel Price of medecine in 1998) is involved in several physiological processes (blood pressure regulation, neurotransmission, cancer cells treatment,….). Nevertheless, NO has also the ability to induce apoptosis (cell death) in healthy cells. Development of site-specific NO donors is therefore beneficial in selective killing malignant cells. Phototriggered NO release provides one such strategy. Our strategy is based on the use of appropriate two photon absorption (TPA) antenna.

[RuIIL5NO]n+/- + H2O -> [RuIIIL5-H2O]n+/- + NO

A recent example of promising system obtained in the group is shown below. It is a complex in which the fluorenyl-terpyridine (FT) ligand is selected as a potential candidate for bringing the ruthenium complex with additional TPA capabilities.

Photoinduced Linkage Isomerisation

These complexes are characterized by the existence of long-lived metastable states (t > 107s) for specific irradiation at a temperature close to ambient temperature. The different states have different Ru-NO conformations which are responsible for a high change in the refractive index, a very important parameter for holographic data storage. [RuCl(py)4(NO)](PF6)2.1/2H2O (py=pyridine) complex studied previously in the group is high of interest because of its complete molecular photoswitching at the solid state.

Our results show that such photochromic composites could be obtained when the complexes are embedded in polymer or silica matrices.

Xerogel of [RuCl(py)4(NO)](PF6)2.1/2H2O, WO 2010/081977 A1 Patent, 22 juillet 2010

NLO Materials

Multi-functional materials and molecular switches have long been a traditional interest of our research. Along this line, the possibility to switch the NLO response of a molecule in an hybrid material by mean of any additional function (e.g. magnetic, conducting or photochromic properties) is investigated. Our expertise is based on computational chemistry, which has become an important tool for providing the efficient guidelines required by synthetic chemistry and physics, to target the microscopic origin of the NLO effects. Among various possibilities, switches can be obtained by :

- Optical effect through the total NLO extinction obtained after Ru-NO -> Ru-ON isomerization in specific molecules selected by computational methods.

- Magnetic effect through a spin crossover phenomenon, in Iron(II) metal complexes, like in the [Fe(Tren)]2+ system shown below, where the magnetic (χM) vs. NLO response (IHRS) correlation is clearly established.

The [Fe(Tren)]2+ cation subjected to a spin crossover phenomenon between 200 and 300 K

These investigations are based on a fruitful network of collaborations (Bordeaux, Valence, Kiev, Mexico).

Organic Materials for Photovoltaics

Organic photovoltaics (OPVs) promise a remarkable cost reduction of photovoltaic (PV) energy, if large improvements of efficiency and lifetime could be achieved. OPV cells are based on Donor/Acceptor molecules. Our previous investigations concerned materials leading to columnar liquid crystal (CLC) structures :

Optical microscopy for CLC complex, in transmission with slightly uncrossed polarizers, observed at room temperature.

These molecules absorb strongly up until near-infrared (NIR). We have been working on nickel bis-dithiolene (Ni-bdt) complexes as new OPV acceptors and we succeeded, by using appropriate ligands, in structuring some of them in hexagonal columnar phases.

X-Ray diffraction pattern (left) of a single domain of (Ni-bdt) which exhibits Bragg peaks characteristic of hexagonal columnar mesophase (right)

We now turn our activities through the design and synthesis of innovative acceptors and low band gap new donor small molecules. We combine experiment (synthesis of materials) and theory (theoretical calculation) in order to optimize the materials. Thanks to new collaborations established with LAAS and LAPLACE Laboratories, we perform thin films engineering and optical/electrical characterizations to set up new photovoltaic cells.

Selected Publications - Patents

2014

"Isolation and characterization of luminescent oxaborinanes. Opening the furan ring attached to a boronic acid group"
Victoria E. González, Felipe Medrano, Mario Rodríguez, Pascal G. Lacroix, Victor Barba.
Tetrahedron Lett., accepted September 2014

"Synthesis, X-ray diffraction analysis and Nonlinear Optical Properties of hexacoordinated organotin compounds derived from Schiff bases."
Blanca M. Muñoz-Flores, Rosa Santillán, Norberto Farfán, Violeta Álvarez-Venicio, Víctor M. Jiménez-Pérez, Mario Rodríguez, Omar G. Morales-Saavedra, Pascal G. Lacroix, Christine Lepetit, Keitaro Nakatani.
J. Organomet. Chem, 2014, 769, 64-71

"Comparative photo-release of nitric oxide from isomers of substituted terpyridinenitrosylruthenium(II) complexes : experimental and computational investigations."
Joëlle Akl, Isabelle Sasaki, Pascal G. Lacroix, Isabelle Malfant, Sonia Mallet-Ladeira, Patricia Vicendo, Norberto Farfán, Rosa Santillan
Dalton Trans, 2014, 43, 12721-12733.

"The Amide bridge in Donor-Acceptor Systems : Delocalization Depends on Push-Pull Stress"
Mauricio, Maldonado-Domínguez, Rafael Arcos-Ramos, Margarita Romero, Blas Flores-Pérez, Norberto Farfán, *Rosa Santillan, Pascal Lacroix, Isabelle Malfant
New J. Chem., 2014, 38, 260-268.

"Heteroleptic bis(cis-1,2-disubstituted ethylene-1,2-dithiolato)nickel complexes obtained by ligand-exchange reaction : Synthesis and Properties"
Thi Minh Ha Vuong, Thanh-Tuan Bui, Alix Sournia-Saquet, Alain Moreau, and Kathleen I. Moineau-Chane Ching
Inorg. Chem., 2014, , 53 (6) 2418-2847

"Chain Ordering of Regioregular Polythiophene Films through Blending with a Nickel Bisdithiolene complex"
D. Hernandez Maldonado, B. Ramos, C. Villeneuve-Faure, E. Bedel-Pereira, I. Séguy, A. Sournia-Saquet, F. Alary, J.L. Heully, K. I. Moineau-Chane Ching
Applied Physics Letters, 2014, , 104 (10) 103302

2013

"Molecular materials for switchable nonlinear optics in solid state, based on Ruthenium-nitrosyl complexes"
Joëlle Akl, Chelmia Billot, Pascal G. Lacroix, Isabelle Sasaki, Sonia Mallet-Ladeira, Isabelle Malfant, Rafael Arcos-Ramos, Margarita Romero, Norberto Farfán.
New J. Chem, 2013, 37, 3518-3527.

"From magnetic to Nonlinear Optical switches in spin-crossover complexes"
P.G. Lacroix, I. Malfant, J.-A. Real, V. Rodriguez
Eur. J. Inorg. Chem., 2013, 615-627

"Compositions of photoswitchable materials"
I. Malfant, B. Cormary
Patent, WO 2013/083920 A1, 13/06/2013

"Medical or therapeutic application of a composite material of ruthenium with a nitrosyl ligand"
I. Malfant, B. Cormary
Patent WO 2013/083921 A1, 13/06/2013

"Towards Bi-functional materials with conducting, photochromic and spin crossover properties"
L. Valade, I. Malfant, C. Faulmann
In "Multifunctional molecular materials", edited by L. Ouahab, Pan Stanford Publishing 2013, 149-184

"Matériaux et quotidien"
Bénédicte Garreau-de Bonneval , Isabelle Hallery, Françoise Milon, Nadia Vujkovic et Katia Fajerwerg Actualité Chimique., 2013,374, 7-12.

2012

"Magnetism and Molecular Nonlinear Optical Second-Order Response Meet ina Spin Crossover Complex"
S. Bonhommeau, P.G. Lacroix, D. Talaga, A. Bousseksou, M. Seredyuk, I.O. Fritsky, V. Rodriguez
J. Phys. Chem. C 2012, 116, 11251-11255.

"Structural Influence on the Photochromic Response of a Series of Ruthenium Mononitrosyl Complexes"
B. Cormary, S. Ladeira, K. Jacob, P.G. Lacroix, T. Woike, D. Schaniel, I. Malfant
Inorg. Chem. 2012, 51(14), 7492-7501.

"Synthesis, X-ray crystal structures, optical properties and modelling data of neutral bis(1,2-dithiolene) nickel complexes of the “non-cyclic SR” family"
Thanh-Tuan Bui, Minh Ha Vuong, Bénédicte Garreau-de Bonneval , Fabienne Alary, Jacob Kane, Carine Duhayon, Alix Sournia-Saquet and Kathleen I. Moineau-Chane-Ching
New J. Chem., 2012,36, 2033-2041

"Trifluoromethyl)trimethylsylane"
Thi Minh Ha Vuong
Syn. Lett., 2012, 23, 1409-1410

2011

"Discotic nickel bisdithiolene complexes : synthesis, optoelectrochemical and mesomorphic properties"
T.T. Bui, O. Thiebaut, , E. Grelet, M.-F. Achard, B Garreau-de Bonneval and Kathleen I. Moineau-Chane-Ching
Eur. J. of Inorg.Chem, 2011, 17, 2635-2676

"Columnar Benzoperylene-Hexa- and Tetracarboxylic Imides and Esters : Synthesis, MesophaseStabilisation and Observation of Charge-Transfer Interactions between Electron-Donating and Electron-Accepting Imides"
J. Kelber, M.-F. Achard, B Garreau-de Bonneval and H. Bock
Chem. Eur. J., 2011, 17 (29), 8145-8155

"Synthesis, Crystal Structures, and Solid State Quadratic Nonlinear Optical Properties of a Series of StilbazoliumCationsCombined with Gold Cyanide Counter-Ion"
Pascal G. Lacroix, M. Carmen Munoz, Ana Belén Gaspar, José Antonio Real, Sébastien Bonhommeau, Vincent Rodriguez, and Keitaro Nakatani
J. Mater. Chem. 2011, 21, 15940-15949.

"Highly Efficient Photorefractive Organic Polymers Based on BenzonitrileShiff Bases Non-Linear Chromophores"
V.M. Herrera-Ambriz, J.L. Maldonado, M. Rodriguez, R. Castro-Beltran, G. Ramos-Ortiz, N.E. Magaña-Vergara, M. Meneses-Nava, O. Barbosa-Garcia, R. Santillan, N. Farfan, F.X. Dang, P.G. Lacroix, I. Ledoux
J. Phys. Chem. C2011, 115, 23955-23963.

"Highly efficient photorefractive polymers doped with cyano nonlinear chromophores"
V.M. Herrera, J.L. Maldonado, M. Rodriguez, G. Ramos-Ortiz, M.A. Meneses-Nava, O. Barbosa-Garcia, R. Santillan, N. Farfan, P. Lacroix
Proceedings of SPIE (2011), 8011(Pt. 3, 22nd Congress of the International Commission for Optics : Light for the Development of the World, 2011), 80115Q/1-80115Q/10.

"The three-dimensional intermolecular network formed via water molecules in trans-bis(nitrito-N)tetrakis(pyridine-N)ruthenium(II) dehydrate"
M. Buron-Le Cointe,B. Cormary, L. Toupet,I. Malfant
Acta Cryst., 2011, C67, m375-m377.

"A facile route for the preparation of nanoparticles of the spin-crossover complex [Fe(Htrz)2(trz)](BF4) in xerogel transparent composite films"
C. Faulmann, J. Chahine, I. Malfant, D. de Caro, B. Cormary and L. Valade
Dalton Trans., 2011, 40, 2480–2485